Flameproof organic fibrous material and composition therefor



Patented Dec. 24, 1946 V FLAMEPROOF ORGANIC FIBROUS MATE- RIAL AND COMPOSITION THEREFOR Osborne Coster Bacon, Penns Grove, N. J assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application December 24, 1943, Serial No. 515,586

11 Claims.

This invention relates to compositions suitable for producing a weather-resistant flameproof finish upon readily combustible fibrous material, such as paper, wood, leather and textiles of ani mal or vegetable origin. This invention further relates to novel, weather-resistant and flameproof fibrous materials produced by the use of said compositions.

For the purpose of tl'iisspeciflcation and the subjoined claims, a flanieproof fibrous material is defined as one which, if tested in a draft-free room by putting in contact with an initiating flame, will not continue to flame of its own accord for more than 5 seconds after removal of said initiating flame, and will not sustain combustion by afterglow beyond the charred area upon removal of said initiating flame.

It will be clear therefore that the material within the above definition may be actually consumed by fire as long as it is in contact with a flame, provided it will not continue to burn after the flame is removed.

Flameproof fibrous materials of the above qualities in gen 'al are not novel. It is old to coat pap-er and t "'iles with heavy metal oxides such as oxides of tin, lead, antimony, arsenic, bismuth, titanium and the like, and to decrease their combustibility thereby. It is also old to impregnate, coat, saturate, or otherwise surface-treat textile fabrics with heavy metal oxides and water-insoluble, chlorine-containing organic compounds having fire and waterproofing qualities. The latter are generally applied from an organic solvent, which sometimes also acts as a vehicle for the metallic oxide.

A full discussion of such chlorine-containing organic compounds is given in the text hereinbelow. All appear to be operative for the purpose in question by virtue of their property of liberating HCl when exposed to intense heat or light, Unfortunately, they retain this behavior, at a very slow rate of course, at ordinary temperatures and under ordinary sunlight as well. The liberated HCl attacks the fibrous material, and as a consequence the latter in due time develops the faulty quality of tendering, that is loss of tensile strength, especially when exposed to weather.

It is accordingly an object of this invention to produce flameproof fibrous material, for instance cellulosic textile material, which shall not develop appreciable tendering in outdoor use. A further object of this invention is to provide coating compositions for achieving the purpose composition of the above nature which is stable against separation of ingredients, and may be handled in commerce and stored for considerable periods for ultimate use by a consumer. Other and further important objects of this invention will appear as the description proceeds.

Now, according to this invention, the aforegoing objects are achieved by incorporating into the flameproofing coating composition, in addition to the metallic oxide and chlorinated organic compounds aforenoted, an anti-tendering agent which is the water-soluble reaction product of formaldehyde upon a mixture of a watersoluble alkaline-amine-proteinate and a reagent of the group which form water-soluble intermediate resins with formaldehyde, such as urea, adipamide, melamine and phenol. Typical re action products of this kind are described in U. S. Patent Nos. 2,262,770 and 2,262,771. In the latter patent aqueous formaldehyde is added to a solution of triethanolamine caseinate containing urea, the quantity of formaldehyde being sufllcient to react first with the solubilized protein and then with the urea. It is stated therein that the urea or its reaction product with formaldehyde exerts a solubilizing action upon the formaldehyde-protein reaction product, wherefore the entire composition is water-soluble and may be diluted considerably without precipitation. Incidentally, I have found that the said reaction products also act as dispersing agents for the other materials in the coating composition, and since they form an insoluble film upon heating above 100 0., they act further as binding agents for the other ingredients, especially pigments where such are employed. These factors enable me to apply the flameproofing composition to the fiber from an aqueous bath, thus obviating the need for organic solvents with their attendant fire hazard, toxicity and high cost. It also gives the entire composition stability against separation or settling, thus enabling my novel flameproof composition to be handled as an article of commerce and to be stored for indefinite periods. Furthermore, the added protein-resin reaction products overcome the sticky finish obtainable with some of the chlorinated organic materials, and they do not affect adversely the flexibility of the treated material at low temperatures.

For simplicity, I shall refer hereinafter to the above reaction product of formaldehyde upon a aforesaid. A still further object is to provide a mixture of an alkaline-amine proteinate and urea aerarea or its equivalent (phenol, melamine, etc.) as the protein-resin reaction product" or proteinresin composition, although it will be clear from the above discussion that the mass is an aqueous suspension containing water-soluble constituents and does not actually become converted into a water-insoluble resin until applied to the fiber and heated to 100 C. or over.

The protein material entering into the composition of the aforegoing protein-resin reaction products may be of either animal or vegetable origin; for example, casein, glue, soyabean protein or zein. All of these are characterized by the common property that they will react with ammonia, quaternary ammonium bases, 01 aliphatic amines, especially polyalkylol amines, to produce compounds soluble in water. I shall refer hereinafter to such compounds as solubilized proteins or as aikaline-amine-proteinates." The other component may be the reaction product of formaldehyde and an amide such as urea or adipamide, formaldehyde and an amine such as melamine, or formaldehyde and phenol.

The chlorine-containing compound employed for flame-proofing may be one of the group consisting of chlorinated paraifin wax, chlorinated fatty acids, chlorinated fish oil, chlorinated vegetable oil, chlorinated rubber, and chlorine-containing resins prepared by polymerizing compounds containing the vinylidine group HzC=C the said compounds having a chlorine content of from 20% to 80%. The flameproofing-property of the treated material generally increases with the chlorine content of the treating agent, although intermediate percentages of chlorine, say 40 to 65%, are preferred in most cases. The metal compound may be antimony trioxide, tetraoxide or pentoxide, tin oxides, bismuth oxides, arsenic oxides or any water-insoluble compound of these metals which will yield the oxide when heated, for instance the respective sulfides or the metals themselves.

In the customary practice with fiameprooflng compositions of the above type, the usual method 7 of application is to disperse the metal oxide in an organic solvent solution of the chlorine-containing compound and apply the mixture in one operation. Such a material corresponds to a solvent-carried paint.

According to my preferred mode of operation the anti-tendering agent of this invention, in other words, the aforesaid protein-resin reaction product, may be employed to produce aqueous suspensions of the aforegoing mixed flameproofing agents, wherein it acts both a a dispersing agent and as a protective bufier against the development of excessive concentrations of hydrogen chloride. However, if desired, the proteinresin buffering agent of this invention and the chlorinated organic fiameprooflng agent above discussed may be applied to the fabric separately, from separate organic solutions or aqueous suspensions.

As already noted, the protective agent of this .invention acts also as a dispersing agent, and as a binding agent for the other ingredients. However, additional, extraneous dispersing agents and binding agents may be added if desired. Likewise, fungicides may be added in the form of insoluble pigments or in the form of compounds soluble in the chlorinated organic agent; again, if desired, they may be added as a separate dispersion. Waterproofing materials may be similarly added when desired.

In addition to the foregoing, any of the customary special agents may be added to the coating composition to achieve special effects such as mildew resistance, rot-resistance, plasticity, coloring, etc. Particularly worthy of note as such auxiliary or special agents are: Salicylanilide (mildew resistance); zinc-dimethyl-dithiocarbamate (mildew and rot-resistance); inorganic coloring pigments such as lead chromate, iron oxides, chrome oxides, and organic pigments such as vat dyes, azo dyes and phthalocyanines; organic colors which are soluble in the chlorinated compound; parafiin wax (waterproofing); and plasticizers such as tricresyl phosphate and the butyl phthalates. Additional buffering agents, for instance water-insoluble calcium or magnesium carbonates may also be added.

The amount of protein-resin reaction product used is usually determined by the amount of dispersing agent needed and the flexibility of the applied film desired.

In general, the four fundamental ingredients of the present fiameprooflng compositions may be varied in amount as follows:

Per cent Protein-resin composition 5 to Metal compound 5 to 40 Chlorine-containing organic compound 10 to 40 Water 5 to 40 They may be applied to the fibrous material in concentrated form (up to 80% solids), or they may be diluted with water. The method of application may be dipping, brushing, spraying, or other means of coating or impregnating. The application to textile fabrics is generally carried out by immersion, squeezing and drying at elevated temperatures. The composition does not need to penetrate deeply to be effective. Good penetration of the interstices of materials such as cotton cloth is desirable when colored compositions are applied. Sufficient penetration is usually obtained when the material i absorbent such as bleached cotton while unbleached cotton is usually resistant to wetting by water and resists penetration.

Agents which lower the surface tension of water may be'added to assist wetting. Alcohols are the preferred wetting assistants, since they do not interfere with the effect of waterproofing agents where such are required. Ethyl alcohol is soluble in water while hexyl alcohol may be dispersed in the composition'or added as a separate dispersion.

The drying step in the? application of these products may be carried out at ordinary temperatures or at temperatures up to 300? F. 'or higher. The higher temperatures are preferred when fastness to water is required. However, considerable fastness to water may be obtained by drying at room temperature.

The compositions of this invention may be applied to any readily inflammable fibrous material such as wool, silk, cellulosic fabrics, ropes, sheets or articles of wood or paper to render them resistant to burning.

Treated materials such as cotton fabrics, paper, rope and wood require varying amounts of added finish to obtain a flameproofing eflect. Heavy weight fabrics can be proofed with less added finish per unit weight than light-weight fabric since the finish does not completely penetrate, and approximately the same amount is required for the same surface area.

Without limiting my invention, the following examples are given to illustrate my preferred mode of operation. Parts mentioned are by weight.

PAar I. PREPARATION or rm: Paornm-Rnsm RzAcnon Pnonocr Example 1 Parts Casein 10 Triethanolamine 4 Urea 18 40% formaldehyde solution; 50 Water 18 Total 100 The above composition was prepared by adding the casein to a solution of the urea and triethanolamine in water, soaking for 15 minutes at about 25 C., heating to about 60 C., then adding the formaldehyde solution at 60 C; and cooling the mixture to room temperature.

Example 2 Parts- Casein Triethanolamine 3.5 Melamine 7.5 40% formaldehyde solution 20 Water 64 Total 100 The above composition was prepared by dissolving 3 parts of triethanolamine in 15 parts of water; adding the casein, allowing to soak for 15 minutes at about 25 C., and then heating to about 60 C. The melamine and the remaining 0.5 part of triethanolamine were added to the formaldehyde solution and likewis heated to about 60 C. The two solutions were then mixed jointly with 49 parts of hot water (60'' C.), and

This composition was prepared by dispersing the casein in 15 parts of water containing the triethanolamine, by soaking, as above, for 15 minutes at about 25 C. and then heating to about 60 C. and adding 47 parts of water at 60 C. followed by the phenol dissolved in the formaldehyde solution also heated to about 60 C., and cooling the mixture.

Example 4 Parts Soyabean protein Triethanolamine 4 Urea 18 40% formaldehyde solution 50 Water 18 Total 100 This composition was prepared in the same manner as Example 1, using soyabean protein instead of the casein in that example. The composition of this example is available in commerce, and was therefore used inmost of the examples of Part II, hereinbelow.

- 6 PA 11. Purmnou or m Fmmnoormc COATING C01IPOSITIOR Example 5.Basic formula Parts Protein-resin reaction-product (from Example 4) 15.5 Antimony oxide (Sb3O3) 20.5 Chlorinated paraflln wax (42% Cl) 43.5 Water I 20.5

Total 100.0

The antimony trioxide was dispersed in the protein-resin agent by high-speed agitation using a soda mixer at room temperature. The chlorinated paraffin wax, containing approximately 42% chlorine, was then added along with 5 parts of water, and dispersed as above. The remaining 15.5 parts of water were then added with stirring. A medium viscosity, white, stable dispersion was obtained.

Example 6.--Variation of the basic formula Parts Protein-resin reaction-product (from Example 4) 15 Antimony oxide 10 Chlorinated paraflin wax (42% Cl.) 50 Water 25 Total The procedure was as in Example 5. A stable dispersion was obtained.

Example 7.Variation of the basic formula Parts Protein-resin reaction-product (from Example 4) 15 Antimony oxide 40 Chlorinated paraflin wax (42% Cl) 20 Water 25 Total 100 Procedure, as in Example 5. A stable dispersion was obtained.

Example 8.Use of a fungicide, calcium carbonate and a waterproofinll a ent The antimony oxide, calcium carbonate and salicylanilide were added to the protein-resin agent in a heavy duty mixer and dispersed by viscous milling; 15 parts of water and the chlorinated paraflin wax were added, and a good dispersion of the wax was obtained by continued milling; 129 parts of water were then added followed by the refined paraffin wax dispersed in 19.2 parts of water containing the glue as a dispersing agent. A stable, fluid, white emulsion was obtained. Fabric treated with this composition was more waterproof than fabric treated with the compositions of Examples 5, 6 and '7.

amazes a Example 9.--Use of a fungicide soluble in the chlorine-containing compound Parts Protein-resin reaction-product (from Example 4) 150 Antimony Oxide 150 Magnesium carbonate 100 Chlorinated paraffin wax (42% Cl) 300 Pentachlor phenol 20 Water 280 Total 1000 The pentachlor phenol was dissolved in the chlorinated parafifin wax and the dispersion was prepared by viscous milling in essentially the same manner as in Example 8. A stable, fluid, white dispersion was obtained.

Example 10.-Use of colored pigments to give a sand shade Parts Protein-resin reaction product (from Example 4) 274.50

Antimony oxide 123.00 Magnesium carbonate 109.00 Lamp black 0.51 Yellow iron oxide 9.22 Red iron 0.77 Chlorinated paraflin wax (42% Cl) 338.00 Water 145.00

Total 1000.00

The pigments and 20 parts of water, followed by the chlorinated parafiin wax, were dispersed in the protein-resin agent by viscous milling. The remaining water was then mixed in. A sand colored, fluid, stable dispersion was obtained.

Example 11..Injra-red, reflecting, olive-drab shade Parts Protein-resin reaction-product 220.0 Antimony oxide 115.0 Zinc dimethyl dithiocarbamate -1- 7.0 Yellow iron oxide 90.0 Red iron oxide 7.0 A blue alkyl ether of dioxydibenzanthrone 24.0 Copper phthalocyanine 6.0 Magnesium carbonate 90.0 Chlorinated parafiin wax (42% Cl) 300.0 Water 141.0

Total 1000.0

The dispersion was prepared by viscous milling. The ingredients were added to the mill in the above order, except that 75 parts of the water wer added intermittently with the magnesium carbonate to maintain the proper viscosity for milling. An olive-drab colored, stable dispersion was obtained.

Example 12 Parts Protein-resin reaction-product 128.0 Lamp black 24.0 Antimony oxide 128.0 Calcium carbonate 118.0 Chrome yellow 65.0 Red iron oxide 11.0 Zinc dimethyl dithiocarbamate 10.0 Chlorinated parafiin wax (42% C1) 354.0 Glue 2.0 Refined paraflin wax 10.0 Water 150.0

Total 1000.0

The dispersion was prepared by viscous milling. The first seven ingredients were mixed in the order named; 20 parts of water were then added; the chlorinated parafiin wax was then added slowly, followed by the refined paraflin wax dispersed in part of the water containing the glue, and finally the remaining water. A stable, liv drab dispersion was obtained.

Example 13.-Incorporating pigments in the 10 chlorine-containing compound Parts Chlorinated parafiln wax (42% Cl) 375.59 Copper phthalocyanine blue 3.22 Chrome yellow 19.32 A brown metallized azo color 6.77 Antimony oxide 170.70 Magnesium carbonate 85.42 Protein-resin reaction-product 338.98

Total 1000.00

All the ingredients except the protein-resin agent were mixed and then ground to a smooth paste by means of a roller-type ink mill. The resulting mixture was then thoroughly mixed with the protein-resin reaction product from Example 4. A stable, olive-drab paste, readily dispersible in water by stirring, was obtained.

- Example 14 Compositions similar to those described in Example 5 were prepared using 15 parts of the reaction products obtained in Examples 1, 2 and 3 as protein-resin compositions. Stable dispersions were obtained.

Example 15.-Use of a casein-urea formaldehyde resin composition in an olive-drab colored flameproofing composition The casein, triethanolamine, urea, formaldehyde and 2.7 parts of water were first combined as described in Example 1. The resulting product was used in place 01 the protein-resin agent from Example 4, and the above composition was prepared in the same manner as in Example 10.

Example 16.Composition containin a vim/lidine chloride polymer Parts Protein-resin reaction-product 12 Antimony oxide 10 Calcium carbonate 10 Lead chrom 6 Lamp blank 25 Red iron oxide 1.0

Water 4 Polyvinylidine chloride dispersion (18% solids) 150 Total.. 195.5

9 The pigments were dispersed in the proteinresln agent and water by means of high-speed agitation. The polyvinylidine chloride emulsion was then added. A stable olive-drab colored dispersion was obtained.

Example 17.-Use of antimony sulfide in place of antimony oxide The antimony sulfide was dispersed in the protein-resin agent and 10 parts of the water by high-speed agitation, followed by the chlorinated paraflin wax and the remaining water. A stable black dispersion was obtained.

Paar In. FLAMEPROOFING Fnmous MATERIAL Example 18.C'otto n duck, Basic formula The compositions obtained in Examples 5, 6 and '7 were diluted with water and alcohol as follows:

Parts Composition of Example 5, 6 or 7 140 Water 50 Denatured alcohol 10 Total"; 200

The diluted treatment baths were applied to unbleached cotton duck, weighing approximately 12 ounces per square yard, by immersing the fabric in the diluted treatment bath, squeezing between rubber rollers to leave in the fabric an amount equal to 80% of the Weight of the fiber, andthen drying on steam heated copper drums at 110 to 115 C. After drying, the samples were found to have gained about 45% in weight.

The resistance to burning of the samples thus prepared was compared with untreated material as follows:

Strips were cut 10 inches warpwise by 2 inches flllingwise and 10 inches fillingwise by 2 inches warpwise. A Bunsen burner, enclosed to exclude drafts, was adjusted to give a luminous flame 1 inches high.

The test strip was suspended vertically with the center of the lower end extending into the above flame of an inch. The strip was allowed to remain in the flame for 12 seconds; it was then removed, and the time that the sample continued to flame was noted. After all burning ceased, the length of char caused by flaming and glowing was measured. The charlength was determined by suspending a weight of 1 pound from one of the legs of the now V- shaped lower end of the sample, raising gently the end of the other leg to support both Weight and sample. thereby causing some tearing at the apex of the V, and then measuring the total depth of the V resulting from both burning and tear.

Resistance to burning was also determined after the treated fabric was subjected to a 24- hour leach by immersion in gently running water at 20-25 C.

The average values of 5 tests for each sample and treatment-bath were as follows:

Flaming time, both before leaching and after leaching 0 to 2 seconds.

10 Char-length, before leachingJnches-- 1% to 1% Char-length, after leaching do 1% to1% Untreated control samples burned up completely under the same tests.

Example 19.In,fra-red reflectant dyed fabric The composition described in Example 8 was applied to burlap colored green and having an infra-red reflectance of about 30% at 800 millimicrons wave length. The composition was diluted with an equal weight of water and applied by immersion, squeezing to 130% liquor take-up, and drying over night in the atmosphere. Another similarly treated sample was dried at, approximately C. Both samples were leached 24 hours by immersion in gently running water at 20-25 C. Osnaburg fabric colored earth red and having an infra-red reflectance of about 25% at 800 millimicrons was treated in the same manner. The shade and infra-red reflectance of the treated samples was only very slightly changed by the treatment. The resistance to burning of all samples was found to be as folows:

Flaming time -seconds 0 Char-length inches 3 to 4 Example 20.Oz en mesh fabric The composition described in Example 10 was diluted with water and denatured alcohol in the following proportions and applied to unbleached cotton netting made on a Levers warp knitting machine and weighing approximately 5 ounces per square yard.

Parts Composition described in Example 10 180 Water 105 Denatured alcohol 15 Total e 300 The netting, approximately 29 feet square, was folded to 8 thicknesses and impregnated with the above mixture by passage through a padding machine equipped with one dip roll in the pad box and two squeeze rolls. The netting was dried at room temperature on a pin frame and then heated in air at to C. for 20 minutes. Samples of the conditioned fabric were tested as follows:

Resistance to burning was determined by burning 0.3 cubic centimeter of absolute alcohol in a cylindrical copper cup Arinch high having a ca- Dacity of 1 cubic centimeter placed under a 7- inch square of the netting held at a 45 angle to horizontal, the bottom of the center of the cup being 1 inches from the center of the test fabric. The size of the burned area was taken as a measure of its resistance to burning.

Other samples of treated netting were leached 24 hours by immersion in gently running water at 25-30 C.

Still other examples of treated netting were exposed for 300 hours in a National weather unit.

The resistance to burning was determined as in the following table.

Treated inches 1 x 2 Treated and leached ..do 1% x 2 Treated and exposed 300 hours in weathering unit inches 1 x 3% Example 21.Paper The composition described in Example 8 was mixed with water and paper pulp and precipitated on the pulp by adding a solution of aluminum sulfate. A sheet of paper was made from the mixture by screening out the pulp and drying the sheet. The finished sheet contained approximately 38.5% chlorinated parafiin wax and 15% antimony oxide. The sheet was very resistant to burning. The same composition was coated on a sheet of paper to give approximately 100% added weight after drying. The product was very resistant to burning.

Example 22.-Wood The composition described in Example was applied to strips of pine wood approximately 12 x 1 x 1 6 inches by dipping the wood in a bath consisting of equal parts of composition and water. The dipped wood was allowed to drain and dry at room temperature. About 12 treated sticks were stacked in the shape of an inverted cone and two paper towels placed under the structure. The paper towels were lighted with a match. This procedure was duplicated with unflameproofing showed excellent flame and char resistance.

Example 26.-C'otton duck. Using antimony sulfide The composition given in Example 17 was applied to cotton duck by dipping, squeezing and drying. Flame tests showed no afterflaming, and

iii

a char-length of one inch.

PABT-IV. Tssrme ms Pnorncrrvn ACTION or THE PROTEIN-RESIN REAGENT Example 27 Weight of added agent in per cent of weight oi fiber S mp1 5 ll ti di 1 11 1 a e on on me um oss Chlorinated Protsresin c 1 1 pp strength parafl. wax react-prod. T

42% 01 (fr. Ex. 4)

Untreated... Control 20 Stoddard solvent 1 63 Water 2i Water and Stoddard solvent 15 Water 17 l A petroleum distillate known to the dry cleaning industry as Stoddard solvent. 1 The protein-resm agent was applied irom water and dried, prior to treatment with chlorinated paraffin from Stoddard solvent.

treated sticks. fire and the paper towels under them burned very slowly. Four additional towels were added without igniting the treated wood. The untreated sticks and the two paper towels under them burned up very rapidly.

Example 23.-Wool A cutting of undyed wool serge fabric was treated with the composition described in Example 8 by immersion, squeezing and drying in air at approximately 90 C. The added dry weight was approximately An untreated strip of the wool fabric burned up completely when tested according to the procedure given in Example 14, while a treated strip was only charred about 1 /2 inches and showed no afterflaming.

Ezample 24.-R egenerated cellulose A sample of light dress material made of regenerated cellulose fibers was treated with the composition described in Example 13 by immersion, squeezing and drying in air at 250 F. The dry take-up on the treated fabric was 40%. The treated fabric was very resistant to burning when tested according to the procedure described in Example 14; the length of char was 2 inches.

Example 25.C'0tton duck. Using a vinylidine type chlorine-containing resin The composition described in Example 16 was applied to cotton duck by dipping, squeezing and drying to give 20% added weight based on the weight of the original dry fabric. A test for The treated sticks did not catch Example 28 In the prior art, it has been suggested to countera/ct the tendering action of flameproofing chlorinated organic compounds by incorporating into the coating composition opaque, inorganic pigments and water-insoluble alkaline materials such as lamp black, zinc oxide, calcium carbonate and yellow iron oxide. To compare the protective action (against tendering of the treated materials) of my novel compositions of this invention against the above compositions of the prior art, the following additional tests were carried out.

Composition B: The same as Composition A, except that the quantity of xylol employed was reduced to 14 parts, and the mixture was emulsifled in water containing 10.0 parts of the proteinrcsin reaction-product obtained in Example 4.

The above compositions were applied to #10 2,41a,1es

duck cotton fabric by immersion, padding and drying to deposit approximately 20% 01' the chlorinated paraflin wax based on the weight of the untreated fabric. The treated fabrics were then exposed in a Fade-Ometer for 50 hours. and the loss in tensile strength due to exposure was determined for the warp threads by comparison with samples of the same treated fabrics before exposure. It was found that the samples treated with Composition A lost 66% of their ori inal tensile strength, while those tested by Composition B suffered no measurable loss whatever.

Example 29 Various cotton fabrics were treated with the compositions prepared hereinabove in Examples 10, 11 and 12, respectively, by immersion, padding and drying to deposit approximately 20% of the chlorinated paraffin wax, based on the weight of the untreated fabric. The treated fabrics were then exposed in a Fade-Ometer for various lengths of time and the loss in tensile strength was determined as above. Found:

Composition oi Type of fabric gg g Loss Hours Per cent Example Tricot netting 200 2 Example 11 Levers netting 100 7 Example 12. Y #10 duck 50 3 in the details thereof may be practiced without departing from the spirit of this invention. Thus, in lieu of the chlorinated paraflin wax and antimony oxide employed in the majority of the above examples, any other combination of known,

practical, fire-resisting materials may be em ployed.

The essential fire-resisting materials of present-day practice are organic compounds containing 20 to 80% chlorine by weight and an oxide of the metals arsenic, antimony, bismuth or tin.

The chlorine-containing organic compounds include chlorinated paraflin wax, chlorinated fatty acids, chlorinated turpentine, chlorinated .paraflin oils, chlorinated vegetable oils, chlorinated rubber, vinyl chloride polymers, chlorinated vinyl chloride polymers, polyvinylidine chloride and other chlorine-containing organic compounds which are unstable at the ignition temperature of cellulosic materials.

It will be recognizedthat all the compounds indicated hereinabove are non-volatile at temperatures up to 300 F.

In all the above, the chlorinated organic compounds found most suitable in our invention are those which possess at least 40% 01' combined chlorine and which are adapted to liberate at least 50% of this combined chlorine in the form of hydrogen chloride upon being heated alone for five minutes at a temperature between 300 and 400 0.. which corresponds to the'average kindling point of untreated paper or'textile fiber.

Organic compounds of lower chlorine content, say 25 to 30%, may also be used, provided larger quantities of the compound are employed. The quantity of any given agent is in general selected so as to give a hydrogemchlorid equivalent not less than a predetermined minimum for any particular type of fibrous material.

According to this invention, the above materials are dispersed in water using a protein= formaldehyde-resin water-soluble reaction prodnot as the dispersing agent, which becomes a water-insoluble film when dried for a long time at ordinary temperatures or for shorter times at higher temperatures. The protein component may be casein, soyabean protein, glue, gelatin or other protein material which is normally rendered water soluble by the aid of alkaline agents and water-insoluble by the action of heat, acids or aldehydes. The alkaline solubilizing agent may be any water-soluble alkaline amine or quaternary ammonium base, although aliphatic amines (especially triethanolamine) are preferred. The most suitable aldehyde is formaldehyde and the most suitable resin base is urea. 'Oth'er resiniorming agents which could be used in lieu of urea are adipamide, succinamide, oxamide or other amides capable of forming water-soluble methylol derivatives which can be insolubilized by condensation to a resinous state. Phenol formaldehyde and melamine formaldehyde may also serve as the resin-forming agent. The essential requirement is that the dispersing-andfilm-forming agent shall prevent the degradation of cellulose treated with an unstable chlozine-containing organic compound. The degrading agent may be chlorine, hydrogen chloride,- hydrochloric acid or metallic chlorides formed from the metallic pigments used.

The compositions described in the examples may be prepared within a wide range of temperatures, say from 32 F. to 212F., although room temperature is preferred for convenience.

The order of addition of the various ingredients of these compositions is not critical except to maintain the optimum conditions for manufacturing, especially consistency, and to obtain a usable product. For example, it is logical to start with at least some of the water and the dispersing agent and then add the materials to be dispersed. It may also be desirable to combine part of the materials in one mix and part in another and then mix the two parts. For example, the metallic oxide may be dispersed along with calcium carbonate and coloring pigments and the dispersion mixed with another dispersion of the chlorine-containing organic material and optionally other ingredients. Where additional water-proofing or mildew-proofing properties are required in a composition, compatible dispersions of either or both of such agents may be added.

Compatible color dispersions may also be added s parately.

The pigments may be ,finely divided to begin with and be easily defiocculated, or it may be necessary to mill or grind the pigments in the vehicle. The pigments may be dispersed in the water phase directly or they may be ground in the chlorinated organic material and the mixture dispersed in the water phase. The water phase may even be dispersed in the oil phase (chlorinated organic compound) at some stage of preparation, although in the final stages, especially when diluted for use, the continuous phase is generally water since dilution tends to invert the water-in-oil" system.

The dispersed compositions may be prepared by any suitable means, such as by viscous milling. grinding in a paint or ink mill, or by high-speed agitation in a more fluid state.

The chlorine-containing material may be a solid dispersed as a pigment, or it may be a liquid at ordinary temperatures and be dispersed in the form of droplets,

The application of the compositions may be carried out under a wide range of conditions of temperature (32 F. to 212 F.), concentration (diluted with water or applied as prepared), and mechanical means of application, such as coating, spreading, brushing, immersion, spraying, etc. The composition may even be precipitated on material from a dilute bath by adding alum or other agents.

The impregnated material may be dried in any suitable manner, although greater durability to water is obtained at higher temperatures and longer periods of drying.

The protective protein-resin may be applied separately to the material to be treated and still be effective in preventing damage by chlorinecontaining materials applied to the same material.

The principal use of the novel compositions of this invention is to render textile fabrics resistant to burning. Materials of most interest are ducks for tents and paulins, and other fabrics such as netting, burlap and Osnaburg, awnings, upholstery, tobacco cloth, and similar materials which may be subjected to leaching by rain, water, exposure to sunlight, and weathering in general. Fabrics not to be exposed to leaching may also be advantageously treated. Treatments are effective on cotton, regenerated cellulose and woolfibers.

The compositions are also useful for treating paper articles, rope, cellulose sponge, padding, stufiing and insulating materials, such as straw and. wood shavings, wood, especially framework for houses and in attics and cellars of completed buildings.

The principal advantages of my novel comr positions are that they will not damage the treated material when exposed to light or heat under normal conditions of use, for instance, prolonged outdoor exposure; they do not contain toxic or inflammable materials; they are applicable from water; they are practically odorless, and the treated materials are non-tacky; the compositions are easily mixed with water, requiring no mechanical equipment for emulsification', and flexible materials remain flexible after treatment, even if subjected to extremely low temperature.

In the claims below the term non-volatile as applied to the chlorine-containing, organic flameproofing agents is to be construed as meaning that the agent will not evaporate at temperatures up to 300 F.

I claim as my invention:

1. An aqueous composition for fiameproofing organic fibrous material, comprising a stable, homogeneous, aqueous suspension of at least three components, namely (1) an inorganic fiameproofing agent, (2) an organic fiameproofing agent and (3) a joint protective and dispersing agent; said inorganic fiameproofing agent being ametai compound of the group consisting of the oxides and sulfides of antimony, arsenic, bismuth and tin; said organic fiameproofing agent being a chlorine-containing, non-volatile water-insoluble, organic compound whose chlorine content is not less than 20% by weight and which liberates at least half of said chlorine, in the form of hydrogen chloride, upon being heated to a temperature between 300 to 400 C.; and said joint protective and dispersing agent being a water-soluble, acid-insoluble reaction product of the group obtained by reacting (a) formaldehyde,

in aqueous medium with (b) a protein which had been rendered water-soluble by reaction with an aliphatic amine and (c) a reagent selected from the group consisting of phenol, melamine, urea and diamides of aliphatic dicarboxylic acids having not more than 6 carbon atoms per molecule; said joint protective and dispersing agent being further characterized by its capacity to form an insoluble film upon being dried, and by its capacity to react with hydrogen chloride which may be slowly liberated by said organic flameproofing material upon storage of the treated fibrous material, thereby counteracting the tendering action which said liberated hydrogen chloride otherwise exerts upon said fibrous material.

2. An aqueous composition for fiameproofing organic fibrous material, comprising a stable, homogeneous, aqueous suspension of at least three components, namely (1) antimony oxide, (2) an organic fiameproofing agent and (3) a joint protective and dispersing agent; said organic flameproofing agent being a chlorinecontaining, non-volatile water-insoluble, organic compound whose chlorine content is not less than 20% by weight and which liberates at least half of said chlorine, in the form of hydrogen chloride, upon being heated to a temperature between 300 to 400 C.; and said joint protective and dispersing agent being a water-soluble, acid-insoluble reaction product obtained by reacting with (a) formaldehyde upon an aqueous mixture comprising (11) a protein solubilized by reaction with an alkanol amine and (c) urea; said joint protective and dispersing agent being further characterized by its capacity to form an insoluble film upon being dried, and by its capacity to react with hydrogen chloride which may be slowly liberated by said organic flameproofing material upon storage of the treated fibrous material, thereby counteracting the tendering action which said liberated hydrogen chloride otherwise exerts upon said fibrous material.

3. An aqueous composition for fiameproofing organic fibrous material, comprising a stable, homogeneous, aqueous suspension of at least three components, namely (1) antimony oxide, (2) an organic fiameproofing agent and (3) a joint protective and dispersing agent; said organic fiameproofing agent being a non-volatile, water-insoluble, chlorinated parafiin hydrocarbon whose chlorine content is between 20 and by weight; and said joint protective and dispersing agent being a water-soluble, acid insoluble reaction product obtained by reacting with formaldehyde upon an aqueous mixture of urea and triethanol-aminesoyabean-proteinate; said joint protective and dispersing agent being further characterized by its capacity to form an insoluble film upon being dried, and by its capacity to react with hydrogen chloride which may be slowly liberated by said organic flameproofing material upon storage of the treated fibrous material, thereby counteracting the tendering action which said liberated hydrogen chlloride otherwise exerts upon said fibrous materia 4. A process of flameproofing organic fibrous 17 material, which comprises impregnating said fibrous material with an aqueous composition of matter as defined in claim 1, and drying the textile material whereby to remove the moisture, and

simultaneously convert the protective agent into a water-insoluble form on the fiber.

5. A process of flameproofing organic fibrous material, which comprises impregnating said fibrous material with an aqueous composition of matter as defined in claim 2, and drying the textile material whereby to remove the moisture, and simultaneously convert the protective agent into a water-insoluble form on the fiber.

6. A process of fiameproofing organic fibrous material, which comprises impregnating said fibrous material with an aqueous composition of' matter as defined in claim 3, and drying the textile material whereby to remove the moisture, and simultaneously convert the protective agent into a water-insoluble form on the fiber.

7. Fibrous organic material impregnated with a fiameproofing composition as defined in claim 1 and as modified on the fiber by drying the impregnated material.

8. Fibrous organic material impregnated with a fiameproofing composition as defined in claim 2 and as modified on the fiber by drying the impregnated material.

9. Fibrous organic material impregnated with a fiameproofing composition as defined in claim 3 and as modified on the fiber by drying the impregnated material.

, 10. An aqueous composition for flameproofing organic fibrous material, comprising a stable, homogeneous, aqueous suspension of at least three components, namely (1) antimony oxide, (2) an organic fiameproofing agent and (3) a joint protective and dispersing agent; said 18 organic fiameproofing agent being polyvinylidene chloride; and said joint protective and dispersing agent being a water-soluble, acid insoluble reaction product obtained by reacting with formaldehyde upon an aqueous mixture of urea and triethanol-amine-soyabean-proteinate; said joint protective and dispersing agent being further characterized by its capacity to form an insoluble film upon being dried, and by its capacity to react with hydrogen chloride which may be slowly liberated by said organic fiameproofing material upon storage of the treated fibrous material, thereby counteracting the tendering action which said liberated hydrogen chloride otherwise exerts upon said fibrous material.

11. An aqueous composition for fiameproofing organic fibrous material, comprising a stable, homogeneous, aqueous suspension of at least three components, namely (1) antimony oxide, (2) an organic flameproofing agent and (3) a joint protective and dispersing agent; said organic fiameproofing agent being chlorinated rubber; and said joint protective and dispersing agent being a water-soluble, acid insoluble reaction product obtained by reacting with formaldehyde upon an aqueous mixture of urea and triethanol-amine-soyabean-proteinate; said joint protective and dispersing agent being further characterized by its capacity to form an insoluble film upon being dried, and by its capacity to react with hydrogen chloride which may be slowly liberated by said organic fiameproofing material upon storage of the treated fibrous material, thereby counteracting the tendering action which said liberated hydrogen chloride otherwise exerts upon said fibrous material.

OSBORNE COSTER BACON. 

